JP2603860B2 - Polymerizable monomer - Google Patents

Description

The present invention relates to an olefin (co) polymer, and more particularly to an optical material having transparency, low birefringence and a high glass transition temperature (Tg). relates olefin (co) pentacyclo [10.2.1.1 ^5,8 .0 ^2,11 .0 ^4,9] hexadeca-6-ene represented by the polymer of (co) useful general formula as a monomer (I).

[Related Art] In recent years, transparent resins have been used as various optical materials. In particular, the field of use of transparent resins excellent in mass productivity as information recording materials is expanding.

Currently, polycarbonate resin, polymethyl methacrylate resin, and the like are used as such optical disk substrate materials. Polycarbonate resin has a high Tg and thus has good heat resistance, but has a slightly high hygroscopicity and a low birefringence. It is easily caused and has hydrolytic properties in molecular structure.
On the other hand, polymethyl methacrylate resin is transparent and has excellent optical properties such as low birefringence, but its high hygroscopicity causes corrosion of the substrate and warpage of the disk surface due to changes in dimensions and shape. I do. Also, since Tg is around 100 ° C., deformation at high temperatures cannot be ignored.

[Problems to be Solved by the Invention] The characteristics required for a resin for an optical disk substrate material, that is, optical properties such as transparency, high light transmittance, stable refractive index, and small birefringence are obtained. Good thing,
As a resin protective layer, it has properties such as aluminum, silver-plated aluminum, etc. that has heat resistance enough to protect the recording substrate, does not discolor, does not corrode the substrate due to moisture absorption, and has good moldability. What,
There is no known resin material capable of satisfying the above conditions.

[Means for Solving the Problems] In view of such circumstances, the present invention has excellent transparency,
Moreover, in addition to optical properties such as being optically homogeneous and having low birefringence, as a (co) monomer of polyolefin resin, it provides a resin material with excellent heat resistance, chemical resistance, dimensional stability and mechanical properties. , pentacyclo represented by the general formula ^{(I) [10.2.1.1 5,8 .0 2,11} .0 4,9] Hekideka 6-
Is to provide en.

Pentacyclo of the present invention [10.2.1.1 ^5,8 .0 ^2,11 .0 ^4,9] hexadeca-6-ene, for example, according to the following reaction formula, tricyclo [6.2.1.0 ^{2, 7]} undeca -4 -En (Liebigs Ann. Chem., 627, 47 (1959), Petroleum chem.
rstry USSR, produced by the Diels-Alder reaction of 1,387 (1962 etc.) (III) with cyclopentadiene (II). This Diels-Alder reaction is a thermal reaction and does not require a catalyst.

In this method, cyclopentadiene may be added to the reaction system as a monomer, or dicyclopentadiene (IV), which is thermally decomposed under the reaction conditions to produce cyclopentadiene (III), may be used as a raw material.

Tricyclo [6.2.1.0 ^2,7 ] undec-4-ene (II
The molar ratio of I) to cyclopentadiene (II) is 1: 1 to 1
The ratio can be 0: 1 (2: 1 to 20: 1 when dicyclopentadiene is used). In general, increasing this ratio also increases selectivity, conversion, and yield, especially at lower temperatures, but increases when the ratio exceeds 5: 1 (10: 1 with dicyclopentadiene). Conversions continue to increase but conversions and yields decrease slightly. Thus, the preferred ratio is 2:
1 to 5: 1 (when dicyclopentadiene is used, 4:
1-10: 1). As the reaction temperature, a temperature between 100 ° C and 300 ° C, preferably a temperature between 200 ° C and 250 ° C can be used. The reaction time varies depending on the reaction temperature, but in each case is 10 minutes to 40 hours, preferably 30 minutes to 30 hours.
In these reactions, it is also possible to add a polymerization inhibitor such as hydroquinone, tert-butylcatechol, or p-phenylenediamine to suppress the formation of a polymer. These reactions may be carried out in a solvent that does not hinder the reaction, such as lower alcohols such as methanol or ethanol, hydrocarbons such as toluene and cyclohexane, and halogenated hydrocarbons such as chloroform and carbon tetrachloride. In carrying out the reaction, any of a batch system, a semi-batch system and a continuous system can be employed.

That the substance thus produced has the structure represented by the formula (I) can be easily confirmed by its ¹ H-NMR and ¹³ C-NMR spectra. Further, the mass spectrum supports the structure of the formula (I).

Example Next, an example will be described.

Example [pentacyclo [10.2.1.1 ^5,8 .0 ^2,11 .0 ^4,9] Synthesis of hexadeca-6-en] tricyclo [6.2.1.0 ^{2, 7]} undec-4-ene (202
g, 1.36 mol), dicyclopentadiene (30 g, 0.227 mol)
Was charged into a 300 ml autoclave, purged with nitrogen, and heated and stirred at 230 ° C. for 10 hours at a maximum pressure of 2.2 kg · cm ⁻² . The reaction mixture was vacuum distilled, pentacyclo as a fraction having a boiling point of ^{107 ℃ / 2mmHg [10.2.1.1 5,8 .0} 2,11 .0 4,9 hexadeca-6-ene (67.3 g, 0.31 mol) was obtained ( Yield 69.3
%).

The CDCl ₃ as a solvent, was measured using TMS as internal standard ¹ H-
As shown in FIG. 1, the chemical shifts of NMR were 0.3 to 2.8 (20H, m) and 6.0 to 6.1 (2H, m).

Similarly, ¹³ C in CDCl ₃ solvent, TMS internal standard conditions
-NMR (complete decoupling, flip angle = 45 °, pulse interval = 10 seconds) chemical shift was 28.92, 29.52, 32.55, 37.48, 41.90, 43.04, 46.12, 48.70, 133.98 as shown in FIG. Was.

 In addition, the result of the mass spectrum is m / e (relative intensity) 214 (18, M +), 147 (44), 119 (17), 105 (6), 91 (15), 79 (17), 66 (100) , 41 (5).

[Copolymerization with Ethylene] A sufficiently dried 500 ml four-neck separable flask was equipped with a stirring blade, a gas blowing tube, a three-way cock, and a thermometer, and the inside was purged with nitrogen. Toluene (150 ml), dichloroethoxyoxovanadium (0.33 mmol), pentacyclo [10.2.
1.1 ^5,8 .0 ^2,11 .0 ^4,9] plus hexadeca 6-ene (12.5 g). A gaseous mixture of ethylene (100 ml / min) and nitrogen (0.45 / min) was passed through a gas injection pipe for 10 minutes while cooling the internal temperature to 5 ° C, and then ethyl aluminum sesquichloride (0.67 mmol) was added to copolymerize. Initiate the reaction,
The copolymerization reaction was carried out at 10 ° C. for 30 minutes while passing the mixed gas. 5 ml of methanol was added to the polymerization solution to stop the copolymerization reaction, the polymerization solution was poured into a large amount of methanol to precipitate a copolymer, and further pulverized and washed in methanol.
After washing with acetone and washing with hexane, vacuum drying was performed at 60 ° C. overnight to obtain a copolymer (6.10 g). According to ¹³ C-NMR analysis, the ethylene composition in the copolymer was 52 mol%, and the Tg measured by DSC was 150 ° C. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.2 g / dl.

Injection molded sample of copolymer obtained by scaling up the same reaction (disc with diameter of 50mm and thickness of 1mm)
Had a Haze of 8% (based on ASTM D1003-52) and a birefringence of 7 nm according to an ellipsometer method (light source wavelength: 830 nm).

[Effects of the Invention] The compound (I) of the present invention is, for example, copolymerized with ethylene in the presence of a catalyst comprising a well-known vanadium compound and a reducing agent such as an alkylaluminum compound to provide transparency, moisture resistance, A resin having excellent light resistance and heat resistance, low birefringence, and no decomposition or gelation upon heating is obtained, and has excellent thermoforming workability.

[Brief description of the drawings]

FIG. 1 shows the ¹ H-NMR spectrum of the polymerizable monomer of the example of the present invention, and FIG. 2 shows the same ¹³ C-NMR spectrum.

Claims (1)

(57) [Claims] 1. The following general formula (I) Pentacyclo [10,2,1,1 ^5,6, 0 ^2,11, 0 ^4,9] consisting hexadeca-6-en-polymerizable monomer represented in.